Ulllted States Patent [19] [11] Patent Number: 5,934,577
Vandenhende et al. [45] Date of Patent: Aug. 10, 1999
[54] PROCESS FOR SEPARATING THE FOREIGN PATENT DOCUMENTS
CONSTITUENTS OF A MUTLILAYER MATERIAL 0581089 2/1994 European Pat. Off. . 0587005 3/1994 European Pat. Off. . [75] Inventors: Bernard Vandenhende, Leest; 4225977 1/1994 Germany ' J ean-Marie YernauX, Rixensart, both 08238440 9/1996 Japan ' of Belgium Primary ExaminerMark Rosenbaum [73] Asslgneei solvay (Soclete Anonyme) Brussels Attorney, Agent, or FirmVenable; George H. Spencer; Belglum John W. Schneller
[21] Appl. No.: 08/972,952 [57] ABSTRACT
[22] Flled: NOV 19 1997 Process for separating the constituents of a multilayer mate [30] Foreign Application priority Data rial including at least one layer of a base plastic (A) and a _ layer of a plastic (B) Which are separated by a layer of Jul. 11, 1997 [BE] Belgium ............................. .. 09700611 adhesive plastic (C), in Which: (1) the material is heated to [51] Int. Cl? ................................................... .. 1302c 19/12 a temperature T1 between the Crystallization temperature of [52] US. Cl. .......................................... .. 241/23; 241/2428 the Plastic B (TC) and TC20 C~> (2) the material is next [58] Field of Search ....................... .. 156/344 241/2418 Shredded by being Subjected to Shearing at aPPrX.imate1y 241/2428 23 24 14_ 209/3 the same temperature, so as to produce delamination and ' thus to convert the material into particles of small dimen [56] References Cited sions of tWo types, some consisting essentially of base plastic (A) and others (Y) consisting essentially of plastic B U.S. PATENT DOCUMENTS and of adhesive plastic (C), and (3) the particles X and Y are 471997109 4/1980 Watanabe ' subsequently separated by electrostatic separation. 4,775,697 10/1988 Schoenhard . 5,366,091 11/1994 Stahl et al. . 14 Claims, N0 Drawings 5,934,577 1 2 PROCESS FOR SEPARATING THE at least one layer of a base plastic (A) and a layer of a plastic CONSTITUENTS OF A MUTLILAYER (B) Which are separated by a layer of adhesive plastic (C), MATERIAL in Which: (1) the material is heated to a temperature T1 betWeen the FIELD OF THE INVENTION crystalliZation temperature of the plastic B (Tc) and The present invention relates to the recycling of multi Tc20 C., layer materials based on plastics. It relates more particularly (2) the material is then shredded by being subjected to to the separation of the constituents of a multilayer material shearing, at approximately the same temperature, so as including at least one layer of a base plastic and a layer of to produce delamination and thus to convert the mate a barrier plastic Which are separated by a layer of adhesive 10 rial into particles of small dimensions of tWo types, plastic. some consisting essentially of base plastic (A) and others (Y) consisting essentially of plastic B and of TECHNOLOGY REVIEW adhesive plastic (C), and Such multilayer materials are commonly employed in (3) the particles X and Y are subsequently separated by very diverse industries, for example in the manufacture of electrostatic separation. Plastic is intended to denote any polymer or polymer packaging materials or of fuel tanks. An example of a multilayer fuel tank comprises 5 layers: PE/adhesive/ mixture. The polymers in question are preferably thermo EVOH/adhesive/PE, Where PE denotes high density poly plastic. Each of the plastics (A, B, C) may in addition optionally contain one or several conventional additives ethylene and EVOH denotes an ethylene-vinyl alcohol copolymer, it being possible for the adhesive to be especially such as stabiliZers, lubricants, antioxidants, pigments, ?ame a polyethylene grafted With maleic anhydride (PE-g-MA). retardants, ?llers or reinforcing ?llers, and the like. Good results have been obtained When the base plastic SUMMARY OF THE INVENTION (A) represents more than 80% of the total Weight of the plastics A, B and C, and in particular more than 90%. During the manufacture of plastics-based articles, espe The base plastic (A) is chosen as a function of the cially by bloW extrusion, a large quantity of scrap is mechanical and/or chemical properties Which the material unavoidably produced (often more than 40%), the recovery must have. Conventional polymers such as polyole?ns or of Which is economically advantageous. The same is even vinyl chloride polymers are generally employed for this more the case Where Whole substandard articles are rejected. purpose. The process according to the invention gives good In the case of multilayer materials the presence of several results When the base plastic (A) consists essentially of one different plastics sometimes presents problems: if it is or more polyole?ns chosen from the homopolymers and deemed sufficient to grind the multilayer material into copolymers of ethylene or of propylene, and in particular of particles and to reemploy them in the manufacture of a neW article, the latter runs the risk of exhibiting mediocre high density polyethylene (HDPE). The process according to the invention is found to be mechanical performance and therefore the quantities of particularly advantageous and ef?cacious When the plastic B material thus recycled must be greatly restricted. It is is a barrier plastic. Abarrier plastic is intended to denote any therefore desirable to have available a simple and effective plastic capable of forming a layer exhibiting a loW perme method enabling the constituents of multilayer materials to ability to particular ?uids such as, for example, be separated With a vieW to being able to reemploy them in hydrocarbon-based fuels. Advantageous crystalline poly a manner Which is comparable With virgin constituents, mers Which have such properties are especially polyamides, Without affecting the performance of the neW articles manu ?uorine-containing polymers and ethylene-vinyl alcohol factured from constituents Which are thus recovered. copolymers. The process according to the invention gives Anumber of methods have already been proposed for this very good results When the plastic B consists essentially of purpose. It is thus especially knoWn to immerse multilayer one or more polymers chosen from polyamides and materials in appropriate organic solvents (for example ethylene-vinyl alcohol copolymers, and very particularly of xylene) at elevated temperature, With a vieW to separating the latter. Plastic B often has a loW adhesiveness to the some constituents by selective dissolving. HoWever, such a conventional polymers of Which the layer of base plastic method requires the use of organic solvents, Which are costly generally essentially consists, and this often makes it nec and generally present safety and environmental problems, essary to resort to an adhesive plastic and a subsequent drying Which is costly in energy. In 50 The adhesive plastic (C) is chosen as a function of the addition, even if the temperature of the solvent is raised, nature of the plastics A and B. A compatibiliZed polyole?n, treatment periods of more than an hour are commonplace. and in particular compatibiliZed polyethylene is frequently These disadvantages are particularly marked When the employed as adhesive plastic The compatibiliZation can articles to be treated are thick, for example fragments of fuel be obtained especially by grafting, in particular by means of tanks. This is because a preliminary optional grinding gen a carboxylic acid anhydride, for example maleic anhydride. erally does not make it possible to reduce the thickness of The adhesive plastic (C) preferably consists essentially of a the particles obtained, and this is detrimental to the rate at polyole?n grafted With maleic anhydride, in particular poly Which they dissolve. Such a solution is therefore not suited ethylene or polypropylene grafted With maleic anhydride. to the treatment of large quantities of material. When the base plastic (A) consists essentially of polyethyl Consequently, the present invention aims to provide a aO ene or of polypropylene the adhesive plastic (C) is advan process Which is simple, fast and efficient, and Which does tageously a grafted polymer of the same kind (PE or PP not require large quantities of solvents to be employed. respectively). Besides the abovementioned 3 layers A/C/B the multi DETAILED DESCRIPTION OF THE layer material subjected to the process according to the INVENTION 5 invention may optionally include one or more other layers of To this end the present invention relates to a process for identical or different nature. It may thus involve especially separating the constituents of a multilayer material including a material of symmetrical structure A1/C1/B/C2/A2, A1 and 5,934,577 3 4 A2 denoting layers of base plastics Which are identical or Similarly, before carrying out the electrostatic separation different (in nature as in thickness), and C1 and C2 denoting (3) it may be useful to remove the ?nes :(microparticles) layers of adhesive plastics Which are identical or different. It produced by the shredding; a conventional device such as an may further involve an asymmetric structure, for example of air classi?er may be employed for this purpose. the A1/C/B/C/A2/A1 type. Another example is that of a The separation (3) of the particles X and Y is performed material comprising several barrier layers, such as A/C/B/ by electrostatic separation. C/A/C/B. Within the electrostatic separation stage a ?rst substage Before the abovementioned stage (1) the process accord consists in charging the particles, for example by corona ing to the invention may optionally include one or more discharge or else by subjecting them to friction. This may conventional stages such as, for example, Washing, or else involve mutual friction, for example in a ?uidiZed bed, or chopping at ambient temperature, intended to reduce the material to fragments of medium dimensions (for example else friction of the particles on a moving member (drum, belt or the like) of an appropriate nature (glass, plastic, or the of the order of a feW centimetres). The heating (1) can be carried out by any knoWn means, like). for example by means of lamps or resistances emitting It is advantageous that after the shredding (2) the particles infrared radiation. The purpose of this heating is to bring the 15 should be charged electrically, With a vieW to electrostatic material to a temperature Which is suitable With a vieW to separation, at a temperature (T3) of at least 50 C. In order shredding to bring the particles into this temperature rangeif they are Stage (2) of the process according to the invention con not yet in itit is possible in particular to employ a sists in shredding the multilayer material at a speci?c conventional heating device such as an infrared lamp. It is temperature. Surprisingly, it has been found that the fact of also possible advantageously to employ a charging equip subjecting the multilayer material to shearing forces at a ment provided With heating elements such as electrical temperature slightly loWer than the crystalliZation tempera resistances. It has been found that When the charging of the ture of the plastic B makes it possible to effect the separation particles Was thus carried out at an elevated temperature, the of, on the one hand, A and, on the other hand B+C. It Will selectivity of the subsequent electrostatic separation could be noted that the separation thus produced is original, insofar 25 be surprisingly improved. An advantage of this alternative as the conventional methods of recycling multilayer mate method, in the context of the Whole process according to the rials comprising a barrier plastic have the objective of invention, is that at the end of the shredding (2) the particles recovering the latter and otherWise yield a generally large are already at an elevated temperature, and this signi?cantly quantity of a mixture of base plastic and of adhesive plastic, reduces the energy required for the abovementioned heating, Which is aWkWard to reexploit directly. In other Words, an as Well as the duration of this heating. Another advantage of important characteristic of the process according to the this alternative method is that it alloWs the actual electro invention is that it is a process Which makes it possible to static separation to be performed With heating, and this has separate the base plastic from the other plastics. This is been found advantageous in the present context. particularly advantageous insofar as, in the majority of It is furthermore desirable that the substage of charging cases, the base plastic (A) represents the mainvconstituent of 35 the particles should take place in an atmosphere of the the material by Weight. Its recovery is therefore economi loWest possible humidity. For this purpose a gas Which has cally important. In fact, even though the barrier plastic is a loW moisture content, for example dry air or an inert gas often more costly, it often represents only a small percentage such as nitrogen, may in particular be injected into the of the total Weight of the material. Thus, in the case of the charging equipment employed. 5 -layer fuel tank described in the introduction, the Weight of According to an alternative form Which has been found EVOH is generally of the order of 3 to 4% relative to the advantageous in this context, after the shredding (2) the total Weight of the tank. particles to be separated are charged electrically by being Another advantage of the process according to the inven brought into contact With a movable member consisting tion is that it can take place in relatively simple equipment, essentially, at least super?cially, of a plastic similar to the Which must, nevertheless, permit the temperature of its 45 adhesive plastic Aplastic similar to the adhesive plastic contents to be precisely controlled. The material is prefer (C) is intended to denote a plastic Which exhibits similar ably shredded in an impeller mill. This type of equipment is triboelectric characteristics. The surface of the movable Well knoWn as such; it generally consists of a rotary drum member preferably consists of a plastic identical With the provided With blades at its periphery, rotating in a vessel to adhesive plastic Which blades are also secured. Amodel capable of producing According to another advantageous alternative form, particles from approximately 5 to 12 mm in siZe is generally Which may be combined With the preceding one, the par chosen, these speci?c dimensions making it possible to ticles to be separated are charged electrically by passing perform the separation With a high efficiency. It is further through a holloW rotary drum provided internally With more advantageous that the knife blades With Which the mill components Which are approximately perpendicular to its is provided should not be too cutting, otherWise the materials 55 internal surface. Such components make it possible to inten Would be cut up Without being subjected to signi?cant sify the friction of the particles on the internal surface of the shearing forces. drum, and this increases their electric charge. Examples of The equipment employed for the shredding (2) is prefer such components Which may be employed are one or more ably used in combination With means for thermal condition rods, small plates and/or paddles Which are approximately ing Which make it possible to maintain the temperature parallel to the axis of the drum. The drum is advantageously therein Within the abovementioned range. In general, the cylindrical in shape; it may, hoWever, have a section other shredding produces additional heating of the material, With than circular, for example polygonal, in particular octagonal. the result that it is often useful to cool the latter, for example The axis of the drum may be horiZontal or slightly inclined With a stream of air at ambient temperature, in order to avoid so as to make it easier for the particles to travel forWard from clustering of the shredded particles. The same device is 65 one end to the other. The angle of inclination and the speed advantageously employed for cooling the particles and for of rotation of the drum alloW the residence time of the removing them, by suction, out of the shredder. particles Within it to be adjusted. 5,934,577 5 6 Once they have been electrically charged, the particles rev/min), the axis of Which Was arranged horiZontally and can be easily separated, in a manner known per se, by falling perpendicularly to that of the ?rst drum. A source of DC betWeen tWo de?ecting electrodes exhibiting a continuous voltage (70 kV) Was connected, on the one hand, to the metal and high potential difference. According to a preferred coating applied to the internal surface of the second drum alternative form the actual separation is performed by depos and, on the other hand, to a metal plate placed laterally iting the precharged particles on the external surface of a facing the second drum, at a distance of 3 to 8 cm. rotary drum Whose axis is horiZontal and Which is connected to a terminal of a DC voltage source, the other terminal A number of trials Were carried out, With mean particle thereof being connected to a de?ecting electrode consisting, throughputs of 30 to 120 kg/h. for example, of a planar plate placed on the side of the said drum, parallel to its axis, generally at a distance of a feW The separation thus produced made it possible to collect, centimetres. In this Way the particles carrying an electric on the one hand, HDPE particles and, on the other hand, charge of opposite sign to the de?ecting electrode Will be particles of EVOH/PE-g-MA mixture, and to do this With an diverted toWards the latter on falling from the drum, and this excellent selectivity, since the HDPE thus recovered exhib alloWs the particles to be separated according to their charge 15 ited a purity of more than 99.5% by Weight. and hence according to their nature. It is preferred that the drum in question should at least super?cially consist of an What is claimed is: insulating material, for example of PVC, its internal surface 1. Aprocess for separating the constituents of a multilayer being provided With electrically conductive means or coat material including at least one layer of a base plastic (A) and ing ensuring a homogeneous distribution of the electric a layer of a plastic (B) Which are separated by a layer of charges. The use of an insulating drum alloWs high electric adhesive plastic (C), comprising steps for: ?elds to be obtained, of the order of 3 to 15 kV/cm, in (1) heating the material to a temperature T1 betWeen the contrast to the knoWn processes employing a conductive drum, With Which the electric ?eld cannot exceed 2 or 3 crystalliZation temperature of the plastic B (Tc) and kV/cm Without leading to a risk of breakdoWn. In the 25 Tc20 C., process according to the invention, When employing an (2) shredding the material by subjecting the material to insulated separating drum, ?elds of 6 to 8 kV/cm have given shearing, at approximately the same temperature, so as very good results. to produce delamination and thus to convert the mate The electrostatic separation is preferably performed With rial into particles of small dimensions of tWo types, heating, the particles being at a temperature of at least 50 some consisting essentially of base plastic (A) and C. others (Y) consisting essentially of plastic (B) and of After separation of the particles X and Y the particles Y adhesive plastic (C), and are advantageously subjected to a subsequent stage (4) of (3) separating the particles X and Y by electrostatic separation making it possible to collect, on the one hand, the separation. plastic B and, on the other hand, the adhesive plastic To 35 2. The process according to claim 1, in Which the base give an example, if the plastic B consists of EVOH, it can be recovered by dissolving the Y particles in a Water/alcohol plastic (A) consists essentially of one or more polyole?ns solution, preferably With heating (for example a Water/ chosen from the homopolymers and copolymers of ethylene methanol mixture at 70 C.). or of propylene. The present invention also relates to a process for recy 3. The process according to claim 1, in Which the plastic cling fuel tanks including at least one layer of a base plastic B is a barrier plastic. (A) and a layer of a barrier plastic (B) Which are separated 4. The process according to claim 1, in Which the plastic by a layer of adhesive plastic (C), or fragments of such B consists essentially of one or more polymers chosen from tanks, in Which the tanks or tank fragments are subjected to polyamides and ethylene-vinyl alcohol copolymers. the process of separation de?ned above. As already 45 5. The process according to claim 1, in Which the adhesive indicated, this process can be applied particularly Well to plastic (C) consists essentially of a polyole?n grafted With tanks in Which the layer(s) of barrier plastic (B) consists maleic anhydride. (consist) essentially of EVOH, the layer(s) of adhesive 6. The process according to claim 1, in Which, after the plastic (C) consisting essentially of PE-g-MA. shredding (2), the particles are charged electrically, With a EXAMPLE vieW to electrostatic separation, at a temperature (T3) of at least 50 C. Fragments of fuel tanks With 5 layers of the HDPE/PE 7. The process according to claim 1, in Which, after the g-MA/EVOH/PE-g-MA/HDPE type Were subjected to the shredding (2), the particles to be separated are charged process according to the invention. These fragments, the electrically by being brought into contact With a movable mean length of Which Was of the order of 10 to 20 cm, Were 55 member having a surface consisting essentially of a plastic ?rst heated to approximately 150 C. and then shredded in similar to the adhesive plastic an impeller mill (of Rapidtrademark, model 3026), at the 8. The process according to claim 1, in Which the particles same temperature. The particles thus obtained, of a mean siZe of approximately 8 mm, Were next charged electrically to be separated are charged electrically by passing through by passing through a holloW rotary drum (length: 100 cm, a holloW rotary drum provided internally With components internal diameter: 40 cm, speed of rotation: 30 to 70 rev/ Which are approximately perpendicular to its internal sur min) arranged horiZontally, the internal Wall of Which Was face. coated With PE-g-MA. The mean temperature Within the 9. The process according to claim 1, in Which, after drum Was approximately 80 C. On leaving this ?rst drum separation of the particles X and Y, the particles Y are the particles Were deposited on the upper generatrix of a 65 subjected to a subsequent stage (4) of separation making it second rotary drum, made of PVC (diameter: 40 cm, length: possible to collect, on the one hand, the plastic B and, on the 40 cm, thickness: 10 mm, speed of rotation: 15 to 50 other hand, the adhesive plastic 5,934,577 7 8 10. The process according to claim 1 wherein said mul some consisting essentially of base plastic (A) and tilayer material is a fuel tank or fragment of said tank others (Y) consisting essentially of plastic (B) and of including at least one layer of a base plastic (A) and a layer adhesive plastic (C), and of a barrier plastic (B) Which are separated by a layer of adhesive plastic 5 (3) separating the particles X and Y by electrostatic 11. A process for recycling a fuel tank or fragment of a separation. fuel tank, including at least one layer of a base plastic (A) 12. The process according to claim 11, in Which the base and a layer of a barrier plastic (B) Which are separated by a plastic (A) consists essentially of one or more polyole?ns layer of adhesive plastic (C), said base plastic (A) repre chosen from the homopolymers and copolymers of ethylene senting more than 80% of the total Weight of plastics (A), 10 or of propylene. (B), and (C), comprising steps for: 13. The process according to claim 11, in Which the plastic (1) heating the material to a temperature T1 betWeen the B consists essentially of one or more polymers chosen from crystalliZation temperature of the plastic B (Tc) and polyamides and ethylene-vinyl alcohol copolymers. Tc20 C., 14. The process according to claim 11, in Which the (2) shredding the material by subjecting the material to 15 adhesive plastic (C) consists essentially of a polyole?n shearing, at approximately the same temperature, so as grafted With maleic anhydride. to produce delamination and thus to convert the mate rial into particles of small dimensions of tWo types, * * * * *